Author Topic: Peracetic in DCM - dreams of success  (Read 9501 times)

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Chromic

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Peracetic in DCM - dreams of success
« on: December 27, 2001, 09:17:00 PM »
In

Post 250498 (missing)

(Chromic: "Re: Chromic's DRAFT peracetic (BIG MISTAKE)", Newbee Forum)
I mentioned having a dream about a peracetic in DCM with anethole. This dream had a happy ending…

A summary of my latest dream:

I watched a gray-haired old man with black-trimmed glasses add 100mmol alkene (14.8g), 150ml DCM to a 500ml flask. 76.1g of 15% peracetic acid (2) buffered with 3g sodium acetate (3) was dripped in over 10 minutes. A mild reflux was present for 5 minutes or so. Then subsided. The reaction was left to stir as the protagonist went off, apparently, into a deep sleep.
 
Perhaps, five or six hours later the main character awoke quite restlessly from his deep sleep, and there I observed him slowly add 150ml of 10% Na2CO3 (NaOH would work too, but Na2CO3 was apparently less expensive to the old man), allowed it to stir, transferred to a sep funnel, drained off organic, then repeated.

The DCM was distilled off (4), 18.8g of oxidation product remained (1), and the oxidation product was put into a standard rearrangement technique.

25ml MeOH were added along with 120ml 15% H2SO4. This was heated to reflux with stirring for 2hrs, extracted 3x with 20ml DCM, washed 2x with 5% NaOH.

After rearranging, a simple distillation was setup, the DCM distilled, then vacuum was applied and this yielded 0.3g clear and colorless forerun at 148C-168C (~5 drops) (likely anethole) and 9.2g slightly yellowish PMP2P at 172-76C. (56.1% yield)

I watched the old man smile with a slight chuckle as I came to consciousness, and decided to quickly jot down some these notes that he telepathically relayed:

(1) if it was solely the glycol this 18.8g of glycol would be 103mmol, which is impossible, and upon no-vac distillation the distillate smells of acetic acid (but the oxidation product does not have this smell), so he had  a good yield of the acetate ester as well. So the sodium acetate buffered version does not produce the epoxide, and in other trials it also appears that adding bicarbonate doesn't allow the epoxide to be formed either... but perhaps some other dreamer will get it to work. Maybe it would be best to try a stronger base like sodium carbonate for the buffering.

(2) 38.4g 35% H2O2, 36.9g acetic acid, 0.8g H2SO4 can be used to prepare 76.1g of 15% peracetic acid. This solution must sit for, preferably, 2-3 days. In fact, he had prepared a large stock solution in advance so he only had to do this once-an old man, but a smart old man. He DID NOT BUFFER his stock solution.

(3) A 2x molar excess of sodium acetate with respect to the sulfuric acid content in the peracetic acid was used to buffer the solution before addition to the flask.

(4) The internal temperature of the flask hit a temperature of over 100C, so I'm sure he distilled off all the DCM, this yield is correct.

(5) PMP2P sinks in water (rather than floats), smells nothing like licorice and tests positive to bisulfite.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #1 on: December 28, 2001, 06:55:00 AM »
I just awoke from another nap, I watched that same pesky old man with the dark-trimmed glasses add 2.5g Na2CO3 (sodium carbonate), 5ml dH2O (distilled water), 23ml MeOH, 5.0g previously-made phenylacetone (pmp2p), and 3.2g (NH2OH)2.H2SO4 (hydroxylamine sulfate) to a flask. He then refluxed the mixture for 2 hrs on a water bath, removed from heat, then added about 15ml dH2O. He allowed it to cool, then moved it to the freezer and suction filtered using saran wrap to push out most all of the solvent possible. He then air dried it, and a white crunchy solid with a mass of 6.6g was obtained (obviously he had some impurities, as this yield is inflated, only 5.5g was expected).

I awoke, quite perplexed by the events in the dream. For what reason would he make anethole ketoxime? Never the less, I carried on through the rest of the day feeling quite refreshed by my nap.

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #2 on: December 30, 2001, 12:43:00 AM »
For the record, acid hydrolysis of the epoxide to form the glycol which is then dehydrated to the ketone is NOT a rearrangement but a hydrolysis/dehydration reaction.  Rearrangement of the epoxide either through the use of heat or lewis acids does not occur via a glycol intermediate.  But I could be wrong.

Rhodium

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #3 on: December 30, 2001, 01:05:00 AM »
According to the articles I have read, epoxide rearrangements using LiBr/LiI involve the lithium salt of the halohydrin, followed by elimination of the halide.

If lithium perchlorate is used, it is said that it involves the lithium alcoholate and a carbonium ion.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #4 on: December 30, 2001, 01:31:00 AM »
Yes, and I also realize the net reaction includes epoxidation followed by acid-catalysed hydrolysis followed with some of the glycol going to form monoacetyl and diacetyls esters by acid-catalysed Fischer esterification, followed by acid-catalysed hydrolysis of some of the oxidation products and finally a Pinacol rearrangement (which probably includes the acid-catalysed dehydration of the glycol as an intermediate, but honestly I'd have to review the Pinacol reaction mechanism) to get the desired ketone (heheh, not to mention the side reactions and unstable intermediates!!!)... but why complicate the language... everyone here understands me, n'est pas? The damn thing worked!

I was very happy to be able to dream about a peracetic acid epoxidation going as it should! That old man had nothing but failures until this reaction, it really brought a smile to my face to see him so happy...  :)

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #5 on: December 31, 2001, 08:51:00 PM »
I just watched the old man slowly add 3.0g of NaOH dissolved in 9mL of water to 5.1g of MeAmCl dissolved in 5mL of water. Was he trying to liberate all of the MeAm before a Al/Hg? Interesting, I've never heard of any one doing that before. He put the solution in the fridge, and went off to work on other tasks.

It looked as if he added 35ml of MeOH, a tiny bit of HgCl2, and let that stir. Then added 2.3g of Al foil, until the solution turned cloudy and the pieces started to float. He then added that solution of freebase MeAm he prepared to the solution, and added 4.5g of PMP2P that I think he prepared in the first dream I had of him. It looked as if NaCl precipitated, and although he was a bit anxious of that interfering, he let the reaction run 5hrs with external heating to keep it at a light reflux, and added 80ml of toluene, washed it once with water, filtered the toluene to remove bits of Al sludge, washed two more times with water, then extracted with distilled water by slowly adding dilute HCl and checking pH as he went (until it was acidic to methyl orange). Before recrystallization, it appears that he got 3.6g of beautiful purple (PURPLE?) (PMMA.HCl, that's a 61% molar yield, the HIGHEST yield this bee has seen so far. The yields from this could have been easily improved by increasing the number of extractions, etc.

Btw, the molar yield of the oxime formation was actually closer to 5.8g after even more drying time.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #6 on: December 31, 2001, 10:47:00 PM »
Another day dream, he recovered 2.8g after recrystallization (all of it went into solution) from 40ml of IPA. The purple color disappeared after recrystallization.

I think he accidentally contaminated the water solution with the slightest bit of methyl orange (by not washing the stir rod he was using to take out samples to daub onto tissue paper wet with methyl orange), and on heating it must have went purple.

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #7 on: January 02, 2002, 03:53:00 AM »
Here's a relevant (old) post by dpHarma:


   dpHarma     [Image] posted 03-03-99 02:49 PM
   Member
               [Click Here to See the Profile for dpHarma]
               ----------------------------------------------------------
               The following is a dream transcribed during a seance
               facilitated by Elton John's road manager.

               A meagre 4.5 gms. performic ketone purified w/ bisulfite,
               was combined w/ 6 gms. MeNH2.hcl in 30ml. MeOH. (the
               MeNH2.hcl was NOT purified of all the ammonium chloride)

               this was stirred by hand until uniform suspension then
               added to prepared amalgam consisting of 6gms. 'pie
               plates' cut into 1cm. squares, 250 mg. HgCl2,
               magnetically stirred and heated for 15 min. in 150ml
               MeOH.

               The ketome/amine was followed by 3.5 gm. NaOH in 5ml. H2O
               and 10 ml. MeOH.

               An reflux condensor was attached to the flask, and
               magnetic stirring and low heat applied for about 18 hrs.
               at which time no Al remnants were visible.

               The soution was quenched with an equal volume of H2O, and
               poured through a plastic kitchen strainer, into a 500ml.
               sep funnel.
               (a small 'gob' of thick putty like Al amalgam was
               recovered in the strainer, and washed and stored under
               peth til next time.)

               The grey liquid was extracted 4 times w/ toluene, the
               aqueous layer set aside, & the toluene extracts washed w/
               H2O, and several sat. NaCl/H2O washes. The washes were
               set aside, and the cleaned tolune was extracted w/ 3 x
               20ml. conc. Hcl in 30 ml H2O.
               The 'spent' tolune was set aside, and the acid sol'n
               washed w/ 3 x 25 ml. DCM.
               the DCM washes were set aside, and the acid sol'n
               basified w/ 25% NaOH until cloudy white ppt. remains. pH
               confirmed w/ bromothymol blue.
               Sol'n. extracted w/ 3 x 25 ml. DCM. The aqueous sol'n.
               was set aside, the DCM extracts washed w/ 1 x 20 ml. H2O,
               2 x sat. NaCl sol'n. dried w/ MgSO4, stripped of DCM by
               boiling off, til nearly gone then adding 25 ml. Toluene.
               about 6 drops of H2O were added, then 1 drop of
               bromoythymol blue as indicator. Conc. hcl was then
               dripped in by eyedropper, with swirling. the small
               aqueous layer changes from 'darkish' to light yellow w/
               each additon and back to dark w/ swirling. Also, as the
               'drop' of acid at the tip of the dropper approaches the
               surface of the tolune mix, 'smoke' (ammonium chloride)?
               appears above the surface. As the end point approaches,
               this effect disapears, and the aq/ layer stays bright
               yellow. stir and swirl vigorously, to ensure all base has
               reacted, then place on heat. boil off all the tolune,
               which should distill most of the water. when the temp of
               the beaker rises, (above 110^C) a slight smoke should
               appear as the toluene vapour ends. remove quickly from
               heat, cool and add an equal volume of cold dry acetone,
               followed by a similar amt. of etO2 (also dry and cold).
               place beaker in dish filled w/ snow (got surplus), and
               stir vigorously. In moments, the layers should cease, and
               a pinkish 'mush' occurs. stirr abit longer, add a bit
               more acetone, stir, decant, repeat. transfer to buchner,
               add acetone, stir, and filter. reapeat til snow white.

               yeild of snow white product from 4.5gm ketone, 3 gms.
               (plus ~200 mg dirty white stuff).

               All of the 'process' solutions were retained, and
               appropriate extractions done, and minimal product
               recovered.

               The extraction of the entire Al sludge provided an
               exceptionally easy and tidy cleanup. Instead of spending
               several hours filtering and re-filtering, the stuff went
               from rxn vessel to xtals under 1.5hrs.

               performing the acid/base routine has two advantages.
               1. it removes any non-basic materials, such as unreacted
               ketone, iso alkene, aldehydes etc., when the acid
               extraction is washed w/ polar solvent.

               2. it removes the base from the relatively large volume
               of tolune used to extract it from the Al/sludge, and
               allows the amt. of solvent boiled off to be kept to a
               minimum.

               3. It provides another level of purification from the
               insidious mercury toxin.

               Thanks to Ritter for his amalgam extraction, and to
               sunlight for his toluene xtallization tip. This is a
               great combination which takes a lot of the drudge out of
               Al/Hg reduction, & workup.

               Now all Elton's roadie's dead uncle has to do is improve
               ketone prep.

               This ? is off topic, but anyways,...

               during the hydrolysis stage of performic, no mention is
               made of stirring. early exps. never stirred during acid
               hydrolysis reflux. the oil kinda swirled and bobbed and
               the dil acid boiled. last time, mag stirring was applied
               about 1/2 way and the mix changed character. w/o
               stirring, it was basically clear. after stirring (and
               heating) for another 1.5 hrs., the acid stayed 'red'!
               even after sitting in the cold for many hours. some
               miscibility occured w/ stirring that didn't without!

               trying to find the point(s) in this process where the
               yeild goes to shit. isoalkene was twice distilled @ atm,
               pressure and 248-252^C.
               Formic acid was concentrated from 65% to >80% by repeated
               treatment w/ anhydrous copper sulfate followed by
               distillation.
               SG went from 1.170 to 1.195. H2O2 was 35%
               40ml acetone used as solvent w/ 32.4gms. isoalkene.

               anybody got the SG of 80, 88 and 90% formic (at 20^C of
               course)???

               dpHarma

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #8 on: January 02, 2002, 04:03:00 AM »
"Extracted with distilled water"?  I don't get it.  How did you isolate your final product?  Evaporation of the water?  How was this accomplished?  And what were the conditions?  (Time, temp, etc.,etc.)

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #9 on: January 02, 2002, 05:50:00 AM »
It makes sense to me, but I'll clarify. Distilled water was added to the organic layer (mdma freebase and toluene), mag stirring started, dilute HCl was added until a sample would turn methyl orange to red. The water separated, and openly boiled off. Then, the product recrystallized.

psychokitty

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #10 on: January 03, 2002, 01:41:00 AM »
Did you separate samples to test or did you simply add the methyl orange directly to the stirred biphasic mixture?

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #11 on: January 03, 2002, 02:18:00 AM »
I watched him add drops of a solution of 1% methyl orange in methanol to filter paper.

He drew out a sample with a stir rod (from the emulsion containing toleune and distilled water) and daubed it to one of the dots of methyl orange on the filter paper. He then titrated some dilute hydrochloric acid, then drew another sample, etc. Obviously he wasn't careful enough to rinse the stir rod off thoroughly as it appears some methyl orange from the filter paper got transferred back into the beaker containing the emulsion. Anyways, after recrystallization all was well.

Good thing it was just a dream, I wouldn't have the faintest idea of what to do with even that little amount of PMMA (other than throw it in the garbage).

I hope he checks into using a similar technique with asarone to attempt tmma-2. If Goiterjoe's peracetic oxidation on asarone did work (which is unknown), then it gives me some hope of his dreams at making tma-2 (sounds good) and tmma-2 (probably a compound just as exciting as pmma... but who knows... gotta try everything once or twice..).

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #12 on: January 15, 2002, 05:09:00 AM »
Just took a quick nap, and noticed the same man attempting the reaction with asarone. He must be crazy to do something like this, I'm almost sure he will fail... but, hey, at least it will answer the question once and for all.

Vibrating_Lights

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #13 on: January 15, 2002, 10:28:00 AM »
any one know the concentration of H2O2 that comes in the wood bleaching kits that also contain the bottle of NaOH solution.
VL_

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #14 on: January 15, 2002, 05:43:00 PM »
Upon waking from a dream about the oxidation, I noticed the man removed lots of reddish-brown crap through 3x 10% NaOH washes. Likely phenolic compounds... let's hope some of the trimethoxys are ok... the suspected product (the monoacetate/diol) is a very viscous oil, looks nothing like his asarone...

VL, wood bleach is usually 30-35%, check the MSDS or call the company.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #15 on: January 17, 2002, 07:53:00 PM »
It appears that after H2SO4 hydrolysis, the old man had a suspected 64mmol crude yield, after simple (and not-careful) vacuum distillation there remained 48mmol of suspected ketone. A very viscous canary yellow oil.

After carefully observing the actions of that man, I believe that it can be said that:

1. the peracetic in dcm does not destroy asarone to tar (as the performic does)
2. the methoxys on asarone are not severely affected by the peracetic acid (they are affected than anethole, but they are not all destroyed).
3. h2so4 hydrolysis does not rip apart the remains from a peracetic to tar or rip off all the methoxys.

The biggest question remaining is, is the suspected ketone truly a ketone, and can it be aminated? We'll have to wait.

noj

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #16 on: January 17, 2002, 07:56:00 PM »
That sounds like what someone has sitting in the freezer. Much more viscous that what someone recalls MDP2P being. Really interested in what you can dream of it.

crucify the ego before it's far too late
and you will come to find that we are all one mind

goiterjoe

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #17 on: January 18, 2002, 12:47:00 AM »
I think asarone ketone is supposed to be a solid, but you would only get that with careful fractional distillation.

If Pacman had influenced us, we'd run around dark rooms eating pills and listen to repetitive music

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #18 on: January 18, 2002, 05:04:00 AM »
Qualified Success!

TMMA-2.HCl should also be a solid, but I watched in the dream the man extract what appeared to be about 6g of a highly viscous oil (with an acid extraction) that was most definitely TMMA-2.HCl (very bitter taste)... I hate it when that happens. Tried to recrystallize, nothing fell out of solution. argh... I hate watching product oil out.

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #19 on: January 19, 2002, 02:46:00 AM »
I watched the man try and form the TMMA-2.sulfate in acetone... the stupid TMMA-2 stayed in the acetone. Oh well, I'll evap it, and add to water and give 40mg to some guinea pigs.

So, is no one interested by this? Peracetic acid, with H2SO4 hydrlolysis works on asarone!? I'm surprised.

goiterjoe

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #20 on: January 19, 2002, 03:27:00 AM »
we're listening, but you haven't convinced us yet that you actually made anything yet.  I hope that you have in fact made what you claimed to, because I've been wonderinng if this reaction works for quite some time now, considering I think I was the first person here to ever attempt it(although I never finished it).  good luck man, and be sure to report back your findings.

If Pacman had influenced us, we'd run around dark rooms eating pills and listen to repetitive music

Antoncho

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #21 on: January 19, 2002, 06:12:00 AM »
But, oh, dear Chromic, of course we are all ears and awaiting impatiently the development of the events. Honestly, i find your work awesome!

Antoncho

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #22 on: January 19, 2002, 09:36:00 AM »
I guess it's little more than the musing of a poor soul slopping together some chemicals in hopes to create something... but hey, play along. I still do not understand why the sulfate and hydrochloride salt "oiled out". Can anyone answer that? I realize it wasn't gassed... but I just don't get it.

foxy2

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #23 on: January 21, 2002, 11:05:00 PM »
Chromic
As Goiter stated how do you know that you have the salt at all?
Bioassy or any other proof?


NoJailForPot

(http://www.nojailforpot.com/)

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #24 on: January 22, 2002, 06:57:00 AM »
The only evidence I have is that it was carried through by an acid/base extraction, and that it liberated hydrogen chloride gas upon adding conc sulfuric acid. It is, without one doubt in my mind, an amine hydrochloride salt. What other amine hydrochloride salt could it be other than TMMA-2.HCl? Can you suggest any sort of qualitative testing that I could do?

Btw, two bioassays at 40mg -(bumped)-> 80mg and 120mg did nothing (not unreasonable), I see no reason to take it higher..

Rhodium

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #25 on: January 22, 2002, 08:51:00 AM »
I assume both salts are very hygroscopic, and that's why they both oiled out. I see a very good reason to take the bioassaying to at least 250mg, and that is to see if there is any activity at all, the Shulgin criteria for something to be inactive is that it is less active than mescaline.

Chromic

  • Guest
TMMA-2 Bioassay
« Reply #26 on: January 27, 2002, 09:49:00 AM »
250mg TMMA-2·HCl handed out to two individuals, SWIM and SWIC. SWIC got mild nausea, infrequent rushes of anxiety, then baseline, mild audio/visual disturbances.. but a definite "something". SWIM got mild nausea, infrequent rushes of anxiety (quickly to baseline) often prompted by audio, delocalization of sounds, mild audio/visual disturbances... both experiences lasted some hours, only +/- through the whole time. The "rushes" were definitely + though, one being ++.

I can't really say if it's active or not.

PoohBear4Ever

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #27 on: January 28, 2002, 06:02:00 AM »
Take two grams, then call me in the morning, mmmK?

;D ,

PB

concoct: 1) to prepare by combining raw materials; 2) to devise or fabricate

Chromic

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #28 on: March 15, 2002, 06:09:00 PM »
I watched the old man run an IR on the TMMA-2. The spectra looks right, it was definitely an aromatic amine and there certainly were no phenolic groups at the end of the day. The yields were poor, but the route is doable. Some of the "oil" was saved and it eventually spontaneously crystallized by itself if you get this "oiling out", don't worry about it.

As requested by others, I'll post my other dreams on PMA.

The old man was seen, a month ago or so, performing a Al/Hg reduction using the above prepared anethole ketoxime. 10 equiv of Al were used in a solvent of 90% EtOH at reflux (note: 10 equiv of AcOH would have really helped this low yield). So to a 100mL flask with a stir bar, 56mL 95% EtOH, 3mL H2O, 0.01g HgCl2, 3.8g Al were added, let amalgamate, 2.5g anethole ketoxime. (acid should have been added in small portions every hour or so) It was slowly brought to a light reflux for a few hours. Then 100mL of 35% NaOH was added and organics extracted with toluene... worked up by washing w/Na2CO3, filtering, washing w/Na2CO3, then extracting by titrating dH2O with HCl(aq).

A 17% yield of PMA.HCl (0.4g from 2.5g ketoxime) was recovered. The PMA.HCl was clean melting, smoky burning, liberates hydrogen chloride with marquis, bitter tasting...

The bioassay confirmed somewhere around 100mg... at 35 minutes the first effects were noted, his pulse was a mere 60bpm but it felt like it was going to explode. After 45 minutes, the old man noticed a definite stimulant effect, his nasal passages cleared up, his appetite went way down, he had major jaw clenching. At 55 minutes he started to experience major stomach upset, drunken, severe dizziness, cross-eyed sort of feeling, tingly all over the body. At about 1:20 his heart was pounding feeling as if it was going to explode, yawning, had a headache... Then about about 1:40 min there was vomitting, MASSIVE MIGRAINE HEADACHE (let's hope that wasn't his brain hemorhaging... heheh... shh... let's NOT think about it, m'kay?). Definite serotonin syndrome, not fun. At about 2:00 he was coming way down, at 3:30 it was over with an "afterglow" feeling.

If you haven't tried PMA, consider yourself lucky.

bicepules

  • Guest
Re: Peracetic in DCM - dreams of success
« Reply #29 on: March 16, 2002, 02:56:00 AM »

     Sounds like a fantastic experience.  Going for martyrdom?  ;D

"No I'll tell you what insanity is, insanity is majority rules"

Chromic

  • Guest
dreams of MDP2P
« Reply #30 on: June 07, 2002, 05:34:00 PM »
SWIC hasn't been sleeping well. He's been having really vivid dreams of an old man stinking up the room with MDP2P. He can't shake that smell out of his head even upon awakening. The same dude seemed to get 36.1g (60% yield) of light yellow MDP2P from 51.8g isosafrole. The funny thing is, I saw him distill the MDP2P  with magnetic stirring but ... WITHOUT A VACUUM ... and it came over at 278-288C, with the majority of it at ~284C.

60% yield of MDP2P using the peracetic after purifing by atmospheric distillation? Fuck yeah! I bet that old man is happy. I bet anyone else who uses this procedure, and purifies the mdp2p with a vacuum could perhaps see yields around 70%.

This time around he used:

Making isosafrole glycol:
51.8g isosafrole, 480ml DCM, 19.5g NaHCO3. Stir bar. Stirring in a cold water bath (no ice). Then added 191.4g peracetic acid (96.7g 35% H2O2, 92.8g HOAc, 1.9g H2SO4 -- sat 7 DAYS... MAKE SURE OF THIS! Your yields will SUCK if you let it sit any less than 4-5 days). Ran 5hrs. Added 320ml 5% NaOH to flask. Stirred. Moved to sep funnel. Drained DCM back into empty flask, dumped aqueous from sep funnel. Added 320ml 5% NaOH to flask. Stirred. Moved to sep funnel. Kept DCM. Distilled off DCM.

Making isosafrole ketone (mdp2p):
Rearranged with 15% H2SO4 w/MeOH for 2hrs. (80ml MeOH, 385g 15% H2SO4, standard extractions & washes) Then proceeded to distill.

If anyone wants more details, SWIC usually sees the man every once and a while in SWIC's sleep and SWIC will do a formal writeup.

Much thanx goes out to RoundBottom for his technique on making isosafrole.  :)  (ie 2x freeze purification, vacuum reflux for a bit, no vac heat/stir, then vac distill.. high quality iso is very easily made this way)

Antoncho

  • Guest
Ah!
« Reply #31 on: June 07, 2002, 07:45:00 PM »
Chromic!

Very cool! :)

Thanx a lot :)

Really have nothing to add, i immediately saved your post on my HD and i'll bee waiting for the more detailed description!



Sincerely,


Antoncho

Rhodium

  • Guest
Chromic: If you do an extended writeup, You'll ...
« Reply #32 on: June 08, 2002, 12:53:00 AM »
Chromic: If you do an extended writeup, You'll end up in my Peracid Oxidation FAQ...

Chromic

  • Guest
Aminates very well!
« Reply #33 on: June 09, 2002, 03:59:00 AM »
The MDP2P was aminated in a similar fashion to the PMP2P and 21.8g MDMA.HCl arose from 23.6g of MDP2P. Plus there's still some (~.5g) crystals stuck to the beaker. It was awesome processing all that ketone comfortably in a 500ml flask. The yield was 72+% from the amination (updated MeAm Al/Hg).

Btw, there is some questions of what to do if you ever see a tar form if you extract with acidic water (instead of gassing). Previously I've said that putting it in the freezer doesn't work, well, it doesn't. But do it anyways, then take a glass rod and scratch side-to-side. Eventually it will form a seed crystal and the holy ball of clear tar will crystalize into nice white crystals. (repeating another A/B will not clear up the tar problem, btw) Alternatively, you can throw a couple of MDMA seed crystals in the tar and it should crystallize that way (or leave it in a dessicator for a week, and it should self-crystallize)

PS. I scrapped away at that beaker for a while.. I'm now up to 23.6g of MDMA... 78+% yield. There's STILL some left in there, but maybe just 200mg or so... not really worth going after as it took about 10-15 minutes to scrap out that 1.8g...

Rhodium

  • Guest
Distill your freebases!
« Reply #34 on: June 09, 2002, 04:29:00 AM »
Are you really encouraging people to skip vacuum distillation of their frerbases? It is of course possible to do without and still get crystals, but just think of how much more pure the product will be - right now every amine (and some other stuff) in the solution will end up in the product, not just the MDMA. I believe that it is worth it going from <95% purity to >99% purity.

Chromic

  • Guest
Well, perhaps.
« Reply #35 on: June 09, 2002, 04:48:00 AM »
The crystals look clean and I'm happy with them. They turn purple-black instantly bubbling HCl when exposed to marquis, taste bitter, fully dissolve into water, have no strong odour and burn cleanly. I'm sure my labrats will love to bioassay this powder for me.

I want to add that vacuum distillation of the freebase, at this time, is not an option for me. Also note that Bright Star, although he includes an A/B, doesn't distill either. And in the MM synthesis there is neither an A/B nor a freebase distillation.

I would not recommend to anyone to skip steps, but these posts show that it's possible to get good quality MDMA from OTC products in high yields. That's something the Oxone procedure never did for me. If possible, vacuum fractional distillation of the ketone would have been preferred over a simple distillation without a vacuum. And sure, vacuum fractional distillation of the freebase would have been preferred over not doing it if I had a high quality vacuum and a large enough amount of freebase to justify it.

Rhodium

  • Guest
Distill or Recrystallize!
« Reply #36 on: June 09, 2002, 07:49:00 AM »
I must edit the MethylMan document immediately - performing an A/B is essential!

Yes, there are writeups out there which skips distillation, and you may get fine white crystals, but as soon as you compare MDMA produced that way with a vacuum distilled batch with GC or HPLC, you will find a lot of things in there which are not MDMA. With your current technique you get crystals of everything that that has an amino group attached, which includes all sorts of dimers and isomers. They may not make any difference for the taste, odour, color tests, solubility or the dubious test of something "burning cleanly". Possibly they may not even affect the high, but any molecule in the product not consisting of MDMA*HCl is in the wrong place, and should have been removed in the first place, as it isn't the psychoactive product we produced to eat/give away.

Recrystallizing the MDMA*HCl (from IPA/Et2O, or Acetonitrile 7ml/g) may give comparable results as with distillation, but this step is usually also skipped.

I condemn any MDMA production not involving a final proper recrystallization of the product or a vacuum distillation of the freebase oil - only a purist would do both, but at least one of them is essential for acceptable purity!

greeter

  • Guest
I must edit the MethylMan document immediately - ...
« Reply #37 on: June 09, 2002, 07:53:00 PM »
I must edit the MethylMan document immediately - performing an A/B is essential!

Rhodium,

    I'm certainly not one to tell you your business, but I think adding the A/B steps in a procedural manner with specific amounts (e.g. add 500ml 5% HCl to ... ) to the MM Al/Hg is a fantastic idea.  I do think though that most bees will eschew the freebase distillation step because the MM procedure if followed exactly yields only 20mL or so of oil.  It has to be run many times or scaled up to produce enough oil to make distillation in larger glass (which I presume most bees have) worthwhile.  I think many bees don't have that much patience when they perceive their bottom dollar profit to be just a gassing away.  Although if freebase distillation becomes de rigueur then new bees just learning will know no other way.

    I think the MM procedure left out the A/B because Ritter in TSII says that after a few washes there is "NO MERCURY CONTAMINATION".  This may(?) be the case but as you point out there is still contamination from other sources.



A watched pot will indeed boil.

Chromic

  • Guest
Well
« Reply #38 on: June 09, 2002, 09:48:00 PM »
Well, for the purposes of the Methyl Man synthesis I think three major changes need to be made with that writeup.

1) on step 17: taking the toluene extract, then washing once with 5% NaOH. Then suction filtering, I think skipping the filtration of aluminum foil chunks is sloppy.
2) on step 19: use 5% NaOH instead of water for the washes (MDMA is thought to be soluble in water). Two more NaOH washes should be enough, followed the one brine wash
3) step 22: provide a link to labtop's directions on how to recrystallize (my favorite):
Recrystallization of *.HCl:
1. Dissolve crystals in the minimum amount of hot, boiling IPA. (10-20ml/1g)
2. If the solution is cloudy, gravity filter, wash the filter paper with hot IPA so you don't
lose any *.HCl.
3. While hot, add 3-4x ice-cold acetone. Let it sit in the freezer until it's ice-cold.
4. Suction filter, wash with tiny amount of ice-cold acetone. The result is virtually pure *.HCl

4) technical correction at end of document: no water is needed for imine formation, the reaction actually produces water

With the Entropy writeup that is attached to the MM document:

Replace his using DCM for toluene. I bet his DCM held a significant amount of MDMA.HCl as it's soluble in DCM. I've tried to gas DCM with failure (then went to extract with water, and low and behold, there's the amine hydrochloride).

And with the Bright Star write up:

1) I think it should be changed to a work up similar to the MM work-up, ie basify the aluminum foil, extract MDMA freebase with toluene
2) An equimolar amount of aq. NaOH should be added to aq. MeAm before adding to the activated foil. (this extra water does NOT hurt the yields, even though the ketone is seen floating in a layer on the bottom) In fact, I think it boosts the yields because the methylamine is now as a gas (ie as Shulgin does it!!!):
"in succession and with swirling, 60 g methylamine hydrochloride dissolved in 60 mL warm H2O, 180 mL
IPA, 145 mL 25% NaOH"
3) preparing the amalgam should consist of adding alcohol with a touch of HgCl2, stirring, then adding the foil to stir until it bubbles. Then add the mixed NaOH/MeAmCl. I hate the water wash technique. It's messy and creates more volume of mercury contaminated wastes.
4) Recrystallization of the methylamine should not be left out of that document

Rhodium

  • Guest
Chromic: Could you be a very nice bee and help me ...
« Reply #39 on: June 09, 2002, 10:30:00 PM »
Chromic: Could you be a very nice bee and help me write the actual updates (what you have written above, plus adding an acid/base extraction to the MM file, perhaps using the one from the BS file) and put them into those documents (just download them from my page, change what needs to be changed, then email me the updated html files)?


Chromic

  • Guest
Sure but a question
« Reply #40 on: June 09, 2002, 11:21:00 PM »
I want to preserve as much of the writing style as possible.. but I'll give it a try with the MM document.

P.S. I do not want to take the priviledge / responsibility of adding an acid/base extraction (ie giving appropriate amounts of solvents for maximal yields) to the MM document. The last thing I want to do is introduce a change that drops the yields. Maybe you could author that part.

Rhodium

  • Guest
Not having followed his procedure myself, I will ...
« Reply #41 on: June 09, 2002, 11:46:00 PM »
Not having followed his procedure myself, I will then only write "Add 25% NaOH solution until clearly basic to pH paper", as using "x ml" of such solutions can be unreliable in practice.

greeter

  • Guest
basification...
« Reply #42 on: June 10, 2002, 02:43:00 AM »
"Add 25% NaOH solution until clearly basic to pH paper"

Can the solution be 'over' basified (i.e. what impact would this have on the final product)?


A watched pot will indeed boil.

Rhodium

  • Guest
No such thing as overbasifying
« Reply #43 on: June 10, 2002, 03:19:00 AM »
No, you cannot really 'overbasify' an MDMA solution, the important part is only to get the pH over about 11, so that all of it is converted to the freebase form so that you can extract it effectively.

Storing a very basic solution of MDMA for extended time periods (24h+) may show more decomposition than if it was less basic, but on a timescales of minutes to a few hours, this is of no importance at all.

Francis_7

  • Guest
A few questions
« Reply #44 on: June 10, 2002, 09:01:00 AM »
Is it the glycol or the epoxide that is formed from the peracetic acid reaction?

Is the peracetic acid added drop by drop or all at once? 

Is this reaction exothermic in any way? 

When distilling the ketone, is there any forerun of epoxide or isoalkene or is the ketone the first and only fraction?

How were you able to control an MM reaction using 25 grams of ketone in a 500 mL flask?  Also, was the reaction performed under stirring?

Could you post or rewrite RoundBottom's isomerization technique here in this thread?  I can't find it.

Chromic

  • Guest
To Francis_7
« Reply #45 on: June 10, 2002, 09:32:00 AM »
The peracetic acid method makes a combination of isosafrole glycol and isosafrole glycol acetate ester. If it's fully buffered and done cold it also can be used to make isosafrole epoxide. In the end, since 15% H2SO4 is used to rearrange, it doesn't matter, and all forms result in isosafrole ketone (MDP2P).

Upon addition of the peracetic acid, there is an exothermic reaction. If a cold water bath is not used, the DCM will come to a boil. If a cold water bath is used, the DCM never heats up enough to boil. There is no need for drastic cooling. I recommend a cold water bath. Less heat means less by products.

The Methyl Man amination was not done. An Al/Hg with MeAmCl was conducted. 23.6g of ketone was processed in a solvent volume of about 300ml. The reduction of nitromethane, not done in this procedure, is normally an extermely exothermic reaction and was avoided for this reason. Also avoided was the large solvent volumes that I feel are a draw back of the MM procedure.

When distilling the ketone there was no forerun of safrole or isosafrole. There was a forerun of DCM up until about 150C or so. A viscous tar remained after the atmospheric distillation. The teflon on the stir bar was also somewhat melted. If this distillation is done repeatedly, you're going to go thru stir bars quickly. (hence my other post on rejuvenating stir bars)

Since the MM amination was not used, the amination was easy to control in a 500mL flask. However, I'm sure the solvent volume of a MM amination could be reduced if 1) thicker aluminum foil was used, getting all the tin foil required into a MM reduction would be a feat if it were Reynold's Heavy Duty wrap 2) an efficient reflux condenser is used.

RoundBottom's variation on the isomerization method proposed by Osmium can be found in

Post 277992

(RoundBottom: "Re: vacuum refluxing", Chemistry Discourse)
and

Post 278285

(RoundBottom: "Re: vacuum refluxing", Chemistry Discourse)
.

Btw, you asked a good set of questions!  :)

greeter

  • Guest
one other MM issue
« Reply #46 on: June 10, 2002, 09:58:00 AM »
I don't know if this is an error or what, but in the MM writeup he says basify the sludge with 35% NaOH solution, then gives a formula of 750mL H2O and 262.5g NaOH.  At least in the terms of solute that I'm used to, this makes about 26% NaOH solution.  262.5 is 35% of 750, not 35% of the total mass of the solution.


A watched pot will indeed boil.

Chromic

  • Guest
Yes, that's an error as well
« Reply #47 on: June 10, 2002, 10:50:00 AM »
>don't know if this is an error or what, but in the MM writeup he says basify the
>sludge with 35% NaOH solution, then gives a formula of 750mL H2O and 262.5g
>NaOH.  At least in the terms of solute that I'm used to, this makes about 26% NaOH
>solution.  262.5 is 35% of 750, not 35% of the total mass of the solution.

Yes. 262.5 / (750+262.5) = 0.259 = ~26%.

A 35% solution would be 262.5g of NaOH and 487.5g of H2O. Preparing a solution that concentrated requires external cooling while mixing the lye and water.

Osmium

  • Guest
When somebody cannot figure out how to perform an ...
« Reply #48 on: June 10, 2002, 12:45:00 PM »
When somebody cannot figure out how to perform an A/B after whatever amination reaction then that person didn't do his/her homework, and isn't ready for synthing anything.

I know that is a very unpopular opinion I am expressing here, but spoonfeeding people like this is not educating anyone. If you tell people every movement of your left pinky during something as simple as an extraction then you are generating a bunch of wanna-bee cooks, not people who understand what they are doing.

(Yes, I HATE 3000 word writeups of reactions when everything necessary can be said in 5 sentences. Awfully hard to read and understand.)

I'm not fat just horizontally disproportionate.

Chromic

  • Guest
Ok... this is really odd!
« Reply #49 on: June 10, 2002, 07:40:00 PM »
I think Entropy's writeup should be axed from the MM document. It's got a few obvious errors.

1) amalgam is not spelt amalgum
2) insufficient purification
3) 50mg (?) of MgSO4
4) Gassing is done in DCM
5) The reaction is done in a BEAKER (!!!)

I can't even attempt to fix that one. Although it's a fun story, this is a haphazardous writeup and probably should be nixed. I'll work on the MM document soon. I'll also incorporate a quick run down of the procedure as Os wants (and similar to the outlines I use).

greeter

  • Guest
Osmium...
« Reply #50 on: June 10, 2002, 09:05:00 PM »
spoonfeeding people like this is not educating anyone

Osmium, NOT spoonfeeding people is certainly not educating them either.  I agree with you that  with more information comes more wannabees, but with more information comes more safety and better technique.  I would much rather hear that some new chemist (such as swim) hurt themselves because they were told to do something and consciously CHOSE to disregard it (i.e. they are an idiot) than to hear that some bee hurt themselves simply because they didn't know what they were doing.

I look at it this way:  In a perfect world, drugs would be legal and easy to obtain, then NONE of us would be making any of these things.  Our toys would be made by highly qualified chemists and with the very best equipment in commercial laboratories.  However, in the world we live in right now, since the drug laws do not seem to reflect common sense, I think the most effective means of bringing about change is to make these drugs ubiquitous.  Already in the States and elsewhere the public opinion of marijuana is changing, simply due to the fact that it is everywhere.

The more chemists that are producing the people that will be doing and that is good for getting people to wake up and write new laws.

Osmium, over and over and over you write the best posts, I've learned so much.  You have truly mastered this art.  If you were to take the time to write a no-nonsense writeup that could be understood even by the most green beginner, imagine how much you would TEACH!!

EDIT:

BTW:  You do write great writeups Os, I just mean to say that if all the good "widely-followed" docs like MM's were written by people like you there would be a lot fewer errors and much better procedure.

Francis_7

  • Guest
You still haven't answered all of my questions
« Reply #51 on: June 10, 2002, 10:02:00 PM »
1.) Was the peracetic acid solution added drop by drop or all at once under cooling? 

2.) Was the amination done under stirring?

Btw, I don't really understand RoundBottom's post.  What is the purpose of applying the vacuum for 30 minutes?  Why not just stir the KOH and alkene for 20 hours at a temp of 160 instead?

Could you please just state what YOU did to make things easier.  Please include all weights and measurements.  RoundBottom's diagram was just plain confusing to me.

One more new question:

1.) What are the ratios of methanol/MeNH2-HCl/Al/ketone and how long did the reaction last before it was time to process the final product?

Here is a link that describes a similar peracetic reaction to yours:

http://l2.espacenet.com/espacenet/bnsviewer?CY=ep&LG=en&DB=EPD&PN=US4393242&ID=US+++4393242A1+I+



Thanks.

Chromic

  • Guest
A perfect world?
« Reply #52 on: June 11, 2002, 02:15:00 AM »
>In a perfect world, drugs would be legal and easy to obtain, then NONE of us would
>be making any of these things.

Really? I disagree. Some of the chemists are here because they are interested in the chemistry and not interested in making any money.

>Was the peracetic acid solution added drop by drop or all at once under cooling? 

It was sitting in the fridge and them poured into the flask.

>Was the amination done under stirring?

Yes. The epoxidation, rearrangement, distillation and amination were all done with magnetic stirring.

> Btw, I don't really understand RoundBottom's post.  What is the purpose of applying
>the vacuum for 30 minutes?  Why not just stir the KOH and alkene for 20 hours at a
>temp of 160 instead?

That's what he does. The initial vacuum is to remove the water present in the KOH, otherwise you're
not going to affect the conversion of safrole to isosafrole and you risk destroying the safrole.

>Could you please just state what YOU did to make things easier.

I recited the general technique in other posts. Freezing and isomerization is hardly rocket science.

>Please include all weights and measurements.  RoundBottom's diagram was just plain confusing to me.

Get him to clarify it then.  :)

>What are the ratios of methanol/MeNH2-HCl/Al/ketone and how long did the reaction
>last before it was time to process the final product?

It went 5hrs.

The reaction details are novel, and are a combination of a variety of information already publically available. No synthesis that I could find uses prepares HOOAc from H2O2/acetic acid and does the oxidation in DCM (to the best of my knowledge). If you want my references for this reaction, I invite you to read:

EP patent 1,140,788

http://l2.espacenet.com/dips/viewer?PN=EP1140788&CY=gb&LG=en&DB=EPD

(pg27)

J Chem Ed, Volume 73 (6), 555 (1996)

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2-phenylpropanal.html



US patent 3,028,398

http://l2.espacenet.com/dips/viewer?PN=US3028398&CY=gb&LG=en&DB=EPD



Organic Syntheses, CV 4, 860

The amination was:
133mmol mdp2p in flask A. 29.8g MeAmCl + 30mL water in flask B. 53ml water + 17.7g NaOH in flask C. In an ice bath, flask C is added to flask B. In a 500ml flask 185ml MeOH, 0.1g HgCl2. Stirred. Added 11.9g Al foil. Left stirring until it starts to bubble. Added flask B then flask A. Rinsed flask A with 10ml MeOH, added to rxn. Let run 5hrs. Basified with 89g NaOH in 210mL water. Extracted with 250ml toluene. Washed with 250ml 5% NaOH. Filtered toluene to remove chunks of foil. Washed with 250ml 5% NaOH. Washed with brine. Extracted with acidic water (titrated to pH 4). Washed with acetone. Took yield. Then went on to recrystallize. (no A/B or freebase distillation was done, I'm sure Rhodium & Osmium disapprove!)

If you need more details, read up more. I think all the essential details have been covered in these posts.

goiterjoe

  • Guest
Isn't it already basic?
« Reply #53 on: June 11, 2002, 02:17:00 AM »
When you run an Al/Hg reductive amination, isn't the resultant slurry already basic from the aluminum hydroxide present?  I thought the purpose of adding that much sodium hydroxide afterwards was just to finish eating up the aluminum and making the mixture easier to separate out.

As far as an A/B extraction, It would be easy to add that step at the end of the writup after the NP extraction.  Just add ~15% hydrochloric acid to your MDMA freebase/NP mixture until acidic, extract the water layer, wash with NP, then add 25% NaOH solution until all of your freebase has separated out.  Then you could take your oil, dissolve it in IPA, and titrate in concentrated hydrochloric acid until neutral.  You could then reclaim your MDMA crystals.  You could further wash them with a NP solvent.

greeter

  • Guest
blip
« Reply #54 on: June 11, 2002, 02:35:00 AM »
Chromic:

    I completely understand about doing it for the love of Chemistry, but are you saying that when it comes to drugs you wouldn't rather be putting some FDA approved USP grade drugs in your body?  I'm not saying there's no need for home Chemistry, it's just that if you could get a pharmaceutical grade tab of MDMA for $5 at the grocery store then what would be the point of creating it yourself (other than maybe once to learn)?  I think doing research chemistry (say synthing analogues) would be much more intriguing (not to mention within the law).  Anyway, $.02 from the peanut gallery.

goiterjoe:

As far as an A/B extraction, It would be easy to add that step at the end of the writup after the NP extraction.

    I think this is what is being talked about (with respect to additions to the MM writeup), but I think it's necessary to do a water wash (at the very least one, maybe even two or three) in addition to carefully filtering the sludge prior to making it acidic.  Otherwise there's just too much grit and sludge in there.



A watched pot will indeed boil.

goiterjoe

  • Guest
That's what I implied
« Reply #55 on: June 11, 2002, 03:20:00 AM »
I was implying that; it would be stupid to skip the bicarbonate washes and water washes.  You would start with the A/B steps right before the MM paper instructs you to gas your product.

Besides, this A/B wash would be just as quick as gassing for recovering crystals, and would be well worth the effort.

RoundBottom

  • Guest
ISO
« Reply #56 on: June 11, 2002, 07:50:00 AM »
um... diagram?  did i write a diagram?  it was a long weekend, pls tell me the post number and i'll try explaining it.

also, chromic is correct about the "sucking" out of the water, that is what SWIM was attempting.  i believe i updated the writeup later on to indicate that i didn't use a column while running the vacuum.  make sure you use a vacuum trap, as it won't help your pump any to suck any water (or solvent) into it.

do it any way you want.  experimentation is just that.

i learned a thing or two from charlie dontcha know.

Rhodium

  • Guest
The PRIDE of being able to
« Reply #57 on: June 11, 2002, 06:56:00 PM »
I'm not saying there's no need for home Chemistry, it's just that if you could get a pharmaceutical grade tab of MDMA for $5 at the grocery store then what would be the point of creating it yourself

Speak for yourself only. If you already have all the lab supplies, the chemicals used for synthesizing 125mg MDMA and purifying it to USP standards are just a few cents, and that's just the economic argument. Then - isn't it something special about knowing that the compound that made the experience for you and your friends possible was a creation of your own mind and own skills?

That's just the beginning - novel analogs are even more exciting, knowing that you are the first human to experience the effects of a certain analog, which is also your own creation - that beats sex and everything else on the planet...

humidbeing

  • Guest
yeah!
« Reply #58 on: June 11, 2002, 08:51:00 PM »
With that staement you've really shown where your
heart lays rhodium!  You're a true believer.

CG I miss you sweety, I really do.

Antoncho

  • Guest
Yes.
« Reply #59 on: June 12, 2002, 02:11:00 AM »

isn't it something special about knowing that the compound that made the experience for you and your friends possible was a creation of your own mind and own skills?





Rhodi...i almost cried when i read this :)

have to confess that for that very reason i'd hate to see certain things to bee government-approved :) ........ :) ......... not for my children, maybee, but definitely for myself..... :)

Sorry for offtopic ;)



Antoncho


Chromic

  • Guest
Amination of peracetic MDP2P to make MDA.HCl
« Reply #60 on: June 12, 2002, 02:39:00 AM »
I watched the crazy old man with the dark trimmed glasses go at it again. This time he fucking amazed me! I saw him do something like 125ml MeOH, 25mL H2O, pinch HgCl2, stirred. 8.9g Al, stirred ~20 mins. Added 6.4g isosafrole ketoxime, added 25g HOAc. ~3 hours pass with mag stirring (flask is only warm to the touch). Slowly added 90g NaOH dissolved in 200mL ice-water. Extracted with 80ml, then 45ml toluene. Washed with 150ml 5% NaOH, filter, 150ml 5% NaOH, 150ml brine. Titrated to pH 4 with HCl in distilled water with stirring. Evaporated water. 5.9g MDA.HCl yield (before recrystallization). (83% crude yield!!!)

The reaction ran HOT and FAST. It was over and done in about two or three hours. The yields are FUCKING STELLAR.

Antibody gets two thumbs up for this procedure!!!

Things learned (this is his third run of ketoxime reduction, btw):

1) you can use MeOH instead of EtOH, which is good news
2) you can amalgamate all the Al before hand and in situ as MM does (very good news!)

This definitely paves the way for OTC MDA.HCl in high yields! (or is it really MDOH.HCl? ahh, who really cares!)

HAPPY, HAPPY, JOY, JOY!!!!!

Btw, the bioassay on the MDMA that the man produced that I wrote about in other posts was predictably good.

Rhodium

  • Guest
How can the statements "flask is only warm to the ...
« Reply #61 on: June 12, 2002, 03:25:00 AM »
How can the statements "flask is only warm to the touch" and "The reaction ran HOT and FAST" be superimposed onto each other? The former being a description of what the flask felt like after 3h?

terbium

  • Guest
A pinch of poison twixt my fingers.
« Reply #62 on: June 12, 2002, 03:26:00 AM »
pinch HgCl2
Shudder!!! You probably shouldn't say it like that. Too many people here are likely to interpret this literally.

Chromic

  • Guest
~50mg
« Reply #63 on: June 12, 2002, 04:19:00 AM »
I'd say I used about 50mg of HgCl2. It was the smallest sizeable bit that comfortable fits on the small end of a spatula tip. The reaction ran hot during the first hour, with a healthly reflux, then petered out quickly. It was over by two hours and was warm to the touch by the third hour. 83% yield is the highest yield I've ever gotten with an Al/Hg. I can't believe it happened with a ketoxime reduction...

Chromic

  • Guest
MDA bioassay
« Reply #64 on: June 14, 2002, 12:43:00 PM »
The MDA/MDMA mixture is phenomenal!

lablozer

  • Guest
What dosage?
« Reply #65 on: June 14, 2002, 04:58:00 PM »

The MDA/MDMA mixture is phenomenal




Was the mix 75mg MDA/75mg MDMA ????

"Balls to the walls" right!



Chromic

  • Guest
As a matter of fact, yes!
« Reply #66 on: June 14, 2002, 05:19:00 PM »
Yes, it was 75/75... it included dreaming while awake, long-lasting buzz, full pupil dilation, intense euphoria... all round it's highly recommended!

Chromic

  • Guest
Next target: asarone
« Reply #67 on: July 02, 2002, 08:05:00 AM »
After success forming MDA & PMA with the peracetic... the next target is using asarone to form TMA-2. Stay tuned! The reaction is running right now and everything looks very promising!

Rhodium

  • Guest
*excited*
« Reply #68 on: July 03, 2002, 12:43:00 AM »
*excited*

goiterjoe

  • Guest
how do you plan on hydrolyzing?
« Reply #69 on: July 03, 2002, 02:17:00 AM »
How do you plan on hydrolyzing the post peracetic results?  Acid hydrolysis fucks it up.

All paths are the same: they lead nowhere

Chromic

  • Guest
H2SO4 acid hydrolysis
« Reply #70 on: July 03, 2002, 05:15:00 AM »
I used H2SO4 rearrangement. What happened was a viscous canary yellow asarone glycol acetate was turned into a light brown viscous sludge. When the sludge is put into bisulfite, I think some crystals form (it's hard to tell -- it's nothing like the bisulfite reaction with PMP2P or MDP2P). I hope to form the oxime to purify it up a bit. I know that distillation without a vacuum leaves nothing worthwhile behind. Distillation of asarone epoxide does not give TMP2P either. (maybe if it's done with a mild  vacuum?)

The sludge can be aminated to TMMA-2 with an methylamine Al/Hg, but since TMMA-2 is worthless (nearly inactive), I hope to form the oxime.

Yes, the yield via this route SUCK, but if I even got a 10% yield of amine from the 150mmol reaction that would be 3.4g of TMA-2 and I'd be jumping for joy!  :)

Rhodium

  • Guest
Try LiI, MgBr2, BF3*Et2O, BiOClO4 or Bi(OTf)3 for ...
« Reply #71 on: July 03, 2002, 06:55:00 PM »
Try LiI, MgBr2, BF3*Et2O, BiOClO4 or Bi(OTf)3 for the rearrangement of the epoxide...

Chromic

  • Guest
Hmm..
« Reply #72 on: July 03, 2002, 08:41:00 PM »
Sounds like a good idea... I think the peracetic in DCM gives the epoxide if it's fully buffered and run at a cool temperature.

Anyways, I'm going to give this a try first. Hopefully I'll be able to form some oxime from the impure crap (and then find a way to purify it). It's just so bloody hot right now... ugh! Too bad I can't work in an air-conditioned lab.  :(

Chromic

  • Guest
Well...
« Reply #73 on: July 04, 2002, 03:01:00 AM »
No oxime crystallized.  :(

This doesn't mean failure (I never would give up so easily), but it sure isn't a good sign. I guess what I'm forced to do is flood with water, then extract with DCM, boil it off, then scratching the tar to crystallize it. Perhaps even that won't work, in which case the project will be abandoned. (with the final saying, "TMP2P  can be made via the peracetic, but in low yields and the clean up is problematic")

I hope not to repeat that sentence anywhere in this thread.

Chromic

  • Guest
Fuck
« Reply #74 on: July 04, 2002, 11:42:00 PM »
I isolated a beige sludge. I'm wondering if I should aminate it or not, might just be a waste of time.

Chromic

  • Guest
Doesn't look good. :(
« Reply #75 on: July 06, 2002, 11:46:00 PM »
I threw 5g of the sludge into an AcOH Al/Hg. I'll have the results tonight or tomorrow. I'm really expecting failure. I'll work the Al/Hg up just the same, but, this story looks to have a sad ending. I really don't believe that asarone glycol or asarone epoxide can be turned into asarone ketone with anything more than very modest yields with H2SO4...  :(  

Besides nitroalkenes and wackers, are there any other techniques for making asarone into a ketone? Or in my desire for another molecule, should I find another alkene to try the peracetic on?

lugh

  • Guest
Classic Route
« Reply #76 on: July 06, 2002, 11:58:00 PM »

Besides nitroalkenes and wackers, are there any other techniques for making asarone into a ketone?



The classic method of making asarone ketone is via the dichloride/dibromide; it's been mentioned here (FSE) and now at:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2p.dibromide.html



Chromic

  • Guest
HOLY SHIT!
« Reply #77 on: July 07, 2002, 03:54:00 AM »
That 5g of sludge that was thrown in, was assumed to be 2.5g pure stuff (and ab2's ratios adjusted). Well, the AcOH Al/Hg went along fast & hard as usual... cooled down... then when it came to extracting, I titrated with dilute hydrochloric acid (using methyl orange as the indicator) then distilled water, then boiled that off. I had ~2.5g of stuff. Then I added about 20ml of MeOH, and boiled it to dissolve the crystals. Then poured off the boiling MeOH (leaving behind some traces of white salts) into an evaporating dish and put it onto the hot plate. Well, I fucked up and spilled about a third of the MeOH onto the hotplate... oops. Heh... my hands are a bit shaky from trying to quit GHB... anyways, I finished evaporating it down, sat it in 10ml of acetone, filtered it and was left with 1.4g!

I don't know about you, but that makes me really happy. I want to make sure everyone hears this:

TMA-2 can be made via the peracetic oxidation & oxime reduction! (*)

I suppose I should bioassay this stuff first, eh? I think my head has had enough amphetamines for a while, so it might take some time to find someone who's willing to sample 100mg of it or so....
(*) Yes, the yields suck in this example. But understand a few things: 1) the ketone was not vacuum distilled 2) the oxime was not properly crystallized 3) the batch size was small, while the glass was big 4) some boiling meoh with amine was lost to the ground

Rhodium

  • Guest
Congratulations! Yet another pioneering synthetic ...
« Reply #78 on: July 07, 2002, 06:08:00 AM »
Congratulations! Yet another pioneering synthetic route... And we have struggled with this off and on for five years to no avail. Now something has finally happened! All that's left is to push the yields over 50% and after that most people should be satisfied.

Chromic

  • Guest
Fuck fuck fuck!
« Reply #79 on: July 07, 2002, 06:55:00 AM »
TAKE AWAY THESE HALLUCINATIONS!

arrgh... they're over powering... it's a definite +3 and I wasn't ready for this kind of trip tonight!

acid_egg

  • Guest
100mgs!!! fuck that was ambitious
« Reply #80 on: July 07, 2002, 07:06:00 AM »
100mgs!!! fuck that was ambitious ::)

Wishing you a happy landing ;)

(rated as:eggsellent)

Rhodium

  • Guest
Aha, that's the key! You are supposed to take ...
« Reply #81 on: July 07, 2002, 08:02:00 AM »
Aha, that's the key! You are supposed to take 100mg or so, rather than following Shulgin's rather conservative dosing... I tried some about 4 years ago a few times, and while there were absolute nothing wrong with the experiences I had, I always thought that the TMA-2 "glow" in a sense has felt very "generic", as in everything visual and/or mental that has to do with its effects mainly consists of all sorts of psychedelic archetypes, where nothing of the experience can be said to be "very typical of TMA-2" or so, everything is just so common (...or at least as common as being in the middle of of a +3 psychedelic experience can be...). With all other psychedelics, there is always a certain personality in the drug I can feel, this just felt I couldn't grasp and classify really. Perhaps the key is more. Before, I regarded Shulgins dosage suggestions more highly than whenever I read on a prescription...

Oh you brave man, we really should be awarding our members some kind of prize (how about a little bronze bee, designed by Fractal or any other of the Hive resident artists?) when they have made a remarkable feat of any kind, as in someone trying out a new drug for the first time on earth (I guess Assholium beats everyone but Shulgin, or devising a new powerful synthetic pathway noone has thought about before (Labtop's NaBH4, Strike's Bubblegum Wrapper, Beaker's NaBH4/CTH reduction)

goiterjoe

  • Guest
congratulations chromic
« Reply #82 on: July 07, 2002, 10:11:00 AM »
you have succeeded where many others have fallen short, myself included.  Now all we need to do is find something to replace the acid hydrolysis step and get the yeilds up.  Hope you get to feeling better by tomorrow.

All paths are the same: they lead nowhere

Chromic

  • Guest
Where the what the fuck am I?
« Reply #83 on: July 07, 2002, 10:41:00 AM »
I feel lost... not sure if I'd recommend this drug to friends... it's quite the eye-opening experience though... I can't FUCKING get over that this is the first psychedelic I've made! Yay for Chromic!

goiterjoe

  • Guest
recommended doses
« Reply #84 on: July 07, 2002, 05:29:00 PM »
Shulgin recommended dosage levels of 20-40mg, with the initial comeon taking an hour and lasting 8-12 hours.  100mg was pretty balls to the walls I bet.  He also says that TMA-2 produces good visuals but without much color enhacement.  This might make it seem dull compared to psylocin or mescaline.

All paths are the same: they lead nowhere

weedar

  • Guest
Time to clean up?
« Reply #85 on: July 07, 2002, 07:05:00 PM »
Chromic,congratulations,hope you feel better now  ;)
May I suggest somebee(Chromic?) make a tidy cleaned-up
write-up of this procedure in another thread?As said earlier,
now it works,next order of business is increasing purity
and yields..

Once again,good work Chromic,a wonder you haven't got a
nifty title yet.. :o

Weedar

Weedar contains 2,4-D dimethylamine salt,apparently

Antibody2

  • Guest
oh comon now
« Reply #86 on: July 07, 2002, 08:27:00 PM »
not sure if I'd recommend this drug to friends. everyone likes to divorce reality once in a while, but you right it isn't for every weekend. way to go amigo

Chromic

  • Guest
Time for a peracetic write up
« Reply #87 on: July 07, 2002, 11:47:00 PM »
I agree, I think it's time to make a proper peracetic write up.

Another bee will have to try and confirm the peracetic on asarone. I fear that I can make no contributions about finding the true yield from this reaction. I don't have a vacuum pump that can distill such a high BP compound. I know the yields are higher than the 5% I got. I'm sure with proper purification that yield could easily push 30%. Also we desparately need someone to try the tosic acid rearrangement on the glycol... perhaps this would give a ketone that is of a higher purity. We also could use someone who could find out if ab2's reduction is making TMOH-2 or TMA-2 (not that it really matters).

And Rhodium, if you're offerring, I'd love a little graphic in place of my "hive addict" title. Anything you would chose should be appropriate.
It's good to be alive.  :)

goiterjoe

  • Guest
nice title... :-D
« Reply #88 on: July 07, 2002, 11:55:00 PM »
nice title... ;D

All paths are the same: they lead nowhere

acid_egg

  • Guest
base jumper
« Reply #89 on: July 08, 2002, 12:00:00 AM »
HaHaHa  ;D I was going to suggest something like alchemical base jumper but this is much funnier LOL! ;D  ;D

Congrats...well deserved! ;)

(rated as:eggsellent)

Rhodium

  • Guest
Graphics and color are unfortunately unavailable ...
« Reply #90 on: July 08, 2002, 12:16:00 AM »
Graphics and color are unfortunately unavailable (those things for Kitty/Pickler took Lili over an hour to hack). The fields are made for alphanumeric strings only.

ClearLight

  • Guest
Oil info...
« Reply #91 on: July 08, 2002, 11:33:00 AM »
Common Name:
 Calamus Oil
 Botanical Name:
 Acorus calamus L.
  
 Geographic origin of the plant:
 Western Nepal
 
Method of growing:
 Wild
 
Introduction / Varity of plant / Method of extraction / Distilled organ:
 The essential oil is obtained by steam distillation of the dried comminuted rhizomes of Acorus calamus L.

 
1. Organoleptic Properties
Appearance
 Slightly viscous liquid
 
Color
 Yellow to yellowish brown
 
Aroma
 Warm woody-spicy
 
2. Physico-chemical Properties
 
Specific gravity
 1.0695 to 1.0795 at 23º C
 
Optical rotation
 
0.2º to
0.5º at 23º C
 
Refractive index
 1.5335 to 1.5589 at 23º C
 
Acid number
 0.6 to 2.5
 
Ester number
 2 to 12
 
Ester number after acetylation
 8.5 to 12
 
Solubility
 Soluble in 0.4 to 1.5 volumes of 80% alcohol
 
3. Uses
(a) In perfumes of the woody oriental type; in spice blends and flavors for alcoholic beverages
 
(b) Medicinal & Aromatherapy use: Calamus causes increased dilation of spleenic vessels, an important factor in regulating blood pressure
 
 
 


Infinite Radiant Light - THKRA

Vibrating_Lights

  • Guest
peracetic
« Reply #92 on: July 08, 2002, 09:53:00 PM »
Can you give some explicate details on your preperation of the peracid?
VL_

Chromic

  • Guest
Yes
« Reply #93 on: July 09, 2002, 04:33:00 AM »
>Can you give some explicate details on your preperation of the peracid?

Yes, and this is an essential detail... mixing the hydrogen peroxide, acetic acid and sulfuric acid must be done at least 3-7 days before you plan to use the peracid. There's not much to it though. Simply mix the three in the ratios given above, and in a few days, you'll notice the mixture has a distinctly different smell (much more acrid and piercing) and it's ready to use.

Antoncho

  • Guest
!!!
« Reply #94 on: July 09, 2002, 06:19:00 PM »
MY SINCERE CONGRATULATIONS, CHROMIC !!!


Antoncho

Vibrating_Lights

  • Guest
Good
« Reply #95 on: July 09, 2002, 06:43:00 PM »
;D  ;)

lablozer

  • Guest
80% acetic acid.
« Reply #96 on: July 10, 2002, 12:04:00 AM »
Is 80% acetic acid fine, instead of GAA? It should be ok... If so, would adding more to reach the equiv of 92.8g HOAc be required?

wacko_reaco

  • Guest
BF3.EtO2 conditions
« Reply #97 on: July 10, 2002, 01:33:00 AM »
Rhodium (or anyone), what conditions would you use to re-arrange the epoxide to ketone using boron trifluoride?

wacka wacka wacka

Chromic

  • Guest
80%
« Reply #98 on: July 10, 2002, 02:39:00 AM »
80% should be fine, but try and ask the supplier to give you glacial acetic acid. They should have no problem fufulling your request.

Rhodium

  • Guest
Wacko: Look up the Bismuth salt rearrangement ...
« Reply #99 on: July 10, 2002, 03:09:00 AM »
Wacko: Look up the Bismuth salt rearrangement articles on my site, in there yu can find references to BF3 rearrangements.

Chromic

  • Guest
Peracetic writeup
« Reply #100 on: August 07, 2002, 05:40:00 AM »
The writeup on the bufferred peracetic oxidation in DCM is now available at

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracetic.chromic.html



Thanks for your support guys!  :)

hCiLdOdUeDn

  • Guest
WOW Chromic, thanks for all your hard work you ...
« Reply #101 on: August 07, 2002, 06:30:00 AM »
WOW Chromic, thanks for all your hard work you put into the writeup. Swim may try peracetic instead of oxone after since the yields are higher and volume is less.

NICE!

hcildoduedn

weedar

  • Guest
Great work Chromic!
« Reply #102 on: August 07, 2002, 03:16:00 PM »
Yet another great method from our favorite self-mutilator ;)

No more use for the Oxone route then?

Weedar

I'm not sure about you guys,but I'm baking brownies!

Chromic

  • Guest
Confirmation of tma-2
« Reply #103 on: August 29, 2002, 06:21:00 PM »
I received this PM a week ago, responded to the sender if it was OK to post it, but no response, so I post it anonymously:

Just wanted to say "Thank you" for your recent work on the peracetic/DCM oxidation. I've been struggling with calamus oil for 2 years now, pseudonitrosite always gave me low yield (5gr TMP2NP from 20gr asarone). I've never been able to aminate this succesfully using Urushibara or Zn, always resulting in a tarry product or nothing.

So I followed your directions on 20 gr asarone but I didn't distill glycol nor ketone, my oxime percipitated as an oil followed by a sloppy amination with Al/Hg. I was really careless throughout the whole process (not my habit, because of former failures didn't really believe in this) and i still got a gram of off-white TMA-2.HCl, after gassing and an acetone wash.

Thanks for your research, it is greatly appreciated! I'm sure this rxn suites asarone perfectly, when the right conditions are there.

SPISSHAK

  • Guest
Are you sure an oxime internediate yeilds an amine
« Reply #104 on: August 30, 2002, 08:55:00 AM »
With Al/Hg reduction?
I've read chem literature for many years, and I don't claim to be elite (because you can never know everything) in the subject which is why I ask this question.
In the literature they attempt to reduce nitroalkenes with Al/Hg under typical conditions (i.e. no acid added, hence basic conditions) and yeild an oxime (unsaturated).
So from what can be infered, if one were to condense a hydroxylamine, to give the oxime, to a ketone and use the aformentioned procedure, logic would say that the hydroxylamine derivitave is produced, and not the saturated nitrogen amime (this compound has psychoactive properties as well) leading one to believe they have the amine when in truth the hydroxylamine is the product.
In typical nitro alkene reductions, acid conditions are employed (presumably to protonate the hydroxlamine, and make it suseptiple to hydrogenation.) so , under these conditions logically the nitro alkene would be reduced to the amine through this hydroxyamine intermediate.
Any one know different, please prove me wrong.


wacko_reaco

  • Guest
reduced solvent trial
« Reply #105 on: August 30, 2002, 02:21:00 PM »
some mother did
200g isosafrole iwas diluted in 200mL DCm and 80g Becarb was added with overhead stirring, the temperature was reduced to 10C with a cold water bath, 800g peracetic acid (made as mentioned aealier and let sit for 5 days) was slowly added over ten minutes, the temperature steadily rose over ten minutes to 33C(also the colour went from colourless to pale yellow) at which time the cold water bath was drained and replaced, the temperature dropped to 26C and the water bath was removed, the temperature rose very slowly to 28C and stayed there. After 4hours, temerature 21C, 400ml of 55 NaOH was added, the solution momentarily went orange and then back to yellow. The majority of the upper layer was poured off and a further 400ml of 5% NaOH was added, this time the orange colour persisted. The aqueous layer was seperated and added to the previous aqueous layer. This aqueous was extracted with 50mL of DCm 9in retrospect i should have evoporated this to see if there was any point, I don't think there was as it was almost colourless). The DCM was distlled off and the glycol taken to 80C, 320mL of MeOH and 1500mL of 15%h2SO4 were added and the solution was reluxed for 2Hrs, heta turned off, stirredf or 15 minutes, then dumped in 2L of ice water, blah blah blah, distilled under vacuum at 140C-155 120mL of yellow oil came over (don't know pressure my gauge is fucked).

Cool huh, that is a ten fold reduction in the DCM

wacka wacka wacka

Chromic

  • Guest
Yes
« Reply #106 on: August 31, 2002, 12:45:00 AM »
>With Al/Hg reduction?

Via a simplified acetic acid Al/Hg a la Antibody2. The acid is apparently necessary to fully reduce the oxime to the primary amine. I've got no way to tell you if TMOH-2 or TMA-2 is made, but the end product will knock your socks off and turn your world upside down.  :)